Process for the polymerization of oxides and catalyst for the polymerization

ABSTRACT

A method for the polymerization of vicinal alkylene oxides using a polymerization catalyst which is the reaction product of an organotin compound (A) with an esterified product (B), the organotin compound (A) containing at least one tin-to-carbon bond in its molecule, and the esterified product (B) being a completely or partially esterified product of oxyacid of phosphorus or derivative thereof, or a combination of reactants capable of forming such ester or derivative.

United States Patent 11 1 Nakata et al. Nov. 20, 1973 PROCESS FOR THEPOLYMERIZATION OF [56] References Cited OXIDES AND CATALYST FOR THEUNITED S T S N S POLYMERIZATION 3,208,955 9/1965 Proops 260/2 [75]Inventors: Tetsuya Nakata, Osaka; Kiyoshige 3,244,646 4/ 1966 Nam et260/2 Kawamata, Itami both of Japan 3,397,155 8/1966 Naro et al.....260/2 3,634,340 1/1972 Gunther 260/2 [73] Assignee: Osaka Soda Co.,Ltd., Osaka, Japan OTHER PUBLICATIONS [221 July 1971 Chemical Abstracts63, 10,072 b (1965) [21] Appl. No.: 160,512

Primary ExaminerWilliam H. Short Relamd Apphcatmn Data AssistantExaminer-E. A. Nielsen Continuation-impart Of S61. NO. 849,519, Aug. 12,Attorney sherman and Shalloway 1969, abandoned.

5 A STRA T [30] Foreign Application Priority Data 7] B 16 1968 J 4358314 A method for the polymerization of vicmal alkylene 1969 Japan44/241 16 oxides using a polymerization catalyst which is the re- 2 iJapan $34163 action product of an organotin compound (A) with an J 3y1969 Japan 44 51159 esterified product (B), the organotin compound (A)Japan 4453391 containing at least one tin-to-carbon bond in its moleu yapan cule and the esterified product (B) being a pletely or partiallyesterified product of oxyacid of g 260,2 252/431 if phosphorus orderivative thereof, or a combination of i g I reactants capable offorming Such ester or derivative [58] Field of Search 260/2 A, 615 B 5Claims, No Drawings 1 PROCESS FOR THE POLYMERIZATION OF OXIDES ANDCATALYST FOR THE POLYMERIZATION This application isacontinuation-in-part of application Ser. No. 849,519 filed on Aug. 12,1969 nowabandoned.

This invention relates to an improvement in the polymerization ofcopolymerization (which may be collectively referred to aspolymerization hereinafter) ofvalkylene oxides, especially vicinalalkylene oxides. More particularly, the invention relates to an improvedmethod for the polymerization of a vicinal alkylene oxide using improvedpolymerization catalysts, themselves and to such catalysts themselves.These catalysts are formed by the reaction of an organotin compound witha complete or partial ester of an oxyacid of phosphorus, a derivativethereof, or a combination of reactants capable of forming such ester orderivative. These catalysts exhibit excellent and high polymerizationactivity at relatively low temperatures, and alsoexcellent stability.Thus the catalysts are easy to handle and allow an advantageousoperation of polymerization. Furthermore, even when they are used inless quantities than those normally required for conventional catalysts,satisfactory results are obtainable, with the consequence that a stillfurther advantage is obtained in that the additional procedure ofeliminating the catalyst from the reaction product can be omitted.'Stillfurther, the catalysts are very excellent in reaction reproducibilityand the intended polymers can be obtained with good qualityreproducibility.

More specifically, this invention relates to a process for thepolymerization of vicinal alkylene oxides, which comprises polymerizingor copolymerizing vicinal alkylene oxides in the presence of aheat-reaction product of (A) an organotin compound and (B) a complete orpartial ester of an oxyacid of phosphorus, a derivative thereof, or acombination of reactants capable of forming such ester or derivative,the organotin compound (A) containing at least one tin-to-carbon bond inits molecule and being selected from the group consisting of thecompounds of the following formulae through:

wherein R is selected from the group consisting of (i) alkyl of one to12 carbon atoms, (ii) alkenyl of two to 12 carbon atoms, (iii) aryl,(iv) aryl substituted by alkyl of one to four carbon atoms,(v).cycloalkyl of three to eight carbon-atoms and (vi) aralkyl; X isselected from the group consisting of hydrogen, halogen, hydroxy,alkoxy, aryloxy, acyloxy, alkylthio, arylthio, alkylthio substituted byalkoxycarbonyl, alkylthio substituted by hydroxy, alkylthio substitutedby acyloxy, alkoxy substituted by alkoxycarbonyl, alkoxy substituted byhydroxy, alkoxy substituted by acyloxy, acyloxy substituted byalkoxycarbonyl, acyloxy substituted by whydroxy, acyloxy substituted byacyloxy, aryloxy substituted by alkyl of one to fourcarbon atoms andarylthio substituted by alkyl of one' to form carbon atoms; a is aninteger of 1 through 4; b is an integer of 4 a; and when a is more than1, Rs may beythe same or different, and when a is 2 and X is selectedfrom the group consisting of alkoxy, acyloxy and alkylthio, the two Xstogether may form a ring:

- wherein R is a member selected from the group consisting of R and X asdefined in formula I, and at least one R is selected from R; X isselected from the group consisting of a carbonate radical, a radical ofan oxyacid of phosphorus, polybasic polycarboxylic acid residues(alkane-di-oyl-oxy and alkane-poly-oyl-oxy), polyhydric alcohol residues(alkylenedioxy), polythiol residues (alkylene dithio),mercaptocarboxylic acid residues (thioalkanoylo y), mercaptoalcoholresidues (thioalkanoxy) and hydroxycarboxylic acid residues(oxyalkanoyloxy); and c is an integer not less than 2 and correspondingto the basicity of the radical X:

R SnY (lll) wherein R is as defined above; Y is a member selected fromthe group consisting of oxygen and sulfur atoms; and d is 1 or 2, andwhen d is 1, e equals 3/2, and when d is 2, e equals 1; it beingpermissible for the compound of formula III to form a complex with acompound of formula I:

R'l-SnR Y +[SnR2 R wherein R is as defined above, and each R is thesame; Y isas defined above; R' is a member selected from the groupconsisting of R and X as defined in formula I and may be the same ordifferent; and l is an integer not less than 1; and

l SnR LMU-l-r v wherein R is as defined above and the two Rs must be thesame; L and L, which may be the same or different, are selected from thegroup consisting of oxygen, sulfur, and

6. Z(OH) PO in which Z is a member selected from the group consisting ofalkyl of one to eight carbon atoms and phenyl;

7. Z H,O)PO in which 2 is as defined above;

in which Z is as defined above;

9. Z(HO) P in which Z is as defined above; and

10. Z (HO)P in which Z is as defined above.

The, the invention also relates to the catalysts described above.

It is known to practise polymerization of alkylene oxides in thepresence of a catalyst, and various catalysts have been proposed forthis purpose.

All of the known catalysts, however, are subject to one or more defects,and a catalyst which is satisfactory in all aspects such aspolymerization activity, stability, facility in handling, quantityrequirement, economic requirement, reaction reproducibility, etc., hasnot yet been proposed. Thus, the art has sought and still seeks such acatalyst, which will allow industrially advantageous practice of thiscatalytic reaction.

While a great many catalysts for the polymerization of alkylene oxideshave been proposed, those receiving the most attention recently are thecatalyst systems composed mainly of two or three organic metal compoundssuch as organic aluminum, zinc, magnesium compounds, etc. lt has beenproved that. organic magnesium effective for compounds are thepolymerization of ethylene oxide, and the catalyst systems composedchiefly of an organic zinc compound are useful almost exclusively forthe polymerization of propylene oxide but they are particularlyineffective for halogensubstituted oxides such as epichlorohydrin.Catalyst systems composed mainly of an organic aluminum compound, forexample, those obtained by reacting an organic aluminum compound with alimited amount of water, can achieve a high degree of polymerization inthe polymerization of great varieties of alkylene oxides. However, theseorganic metal catalysts inclusive of those from mangesium and zinc, areby no means suitable for industrial use, because they are hazardous inhandling and expensive and because they must be used in relatively largeamounts in order to attain sufficient catalytic effects. For thesereasons, development of a novel and improved catalyst has been greatlydemanded in the art.

Various attempts have been made to polymerize alkylene oxides in thepresence of metallic compounds other than organic metal compounds. Withregard to tin compounds, the use of a complex of tin halogenide with adiamine has been proposed (German Pat. NO. 55,431,1967), the use ofstannous carboxylate has been proposed (U.S. Pat. No. 2,933,459) and theuse of a reaction product between stannous chloride and an alkyleneoxide has been proposed (US. Pat. No. 3,248,347).

Techniques using phosphorus compounds have also been proposed. Forinstance, the use of phosphoric acid salts of melts such as titanium,zirconium, thorium, lead, vanadium, chromium, manganese, iron, etc hasbeen proposed. (Chemical Abstracts, 63, 10,071 h l0,072 b (1965) the useof a reaction product between phosphoric acid and a halide of a metalsuch as aluminum, gallium, indium, thallium, boron, etc has beenproposed (U.S. Pat. No. 3,397,155), and the use of a reaction productbetween phosphoric acid and an alkoxide of a metal such as aluminum,gallium, indium, thallium, boron, etc has been proposed (US. Pat. No.3,244,646).

These tin or phosphorus compounds are objectionable, however, in,thatthe resulting polymers fail to have a high molecular weight, thecatalyst activity is not applicable generally to alkylene oxides, andthey must be used in large quantities.

Organotin compounds are very stable, unlike the above-mentioned organiccompounds of metals of Groups II and 111, but there is substantially noinstance of using organotin compounds as polymerization catalysts. Onlytheir polymerization activity for ethylene oxide was recently examinedand the result was reported only as to dialkyltin dihalides. Morespecifically, it was reported that the polymerization of ethylene oxidein the presence of such organotin compound gives only a colored,wax-like low molecular weight polymer, though conducted under verysevere conditions (J. Chem. Soc. Japan, Industrial Chemistry Section,71, 2,054 (1968) Research has been conducted with a view to developingcatalysts for polymerization of alkylene oxides, which will meet all ofthe foregoing requirements, and it has now been found that reactionproducts between the above-mentioned organotin compound (A) and thespecific phosphorus oxyacid ester component (B) selected from a completeor partial ester of an oxyacid of phosphorus, a derivative thereof and acombination of reactants capable of forming such ester or derivative,can exhibit an excellent catalytic activity for polymerization ofalkylene oxides and are satisfactory in all of the above-mentionedrequirements.

Accordingly, the primary object of this invention is to provide acatalyst for polymerization of an alkylene oxide, especially a vicinalalkylene oxide, which is industrially satisfactory in all such respectsas polymerization activity, stability, facility in handling, amount ofuse, reaction reproducibility, etc., and to provide a process for thepolymerization of an alkylene oxide, especially a vicinal alkyleneoxide, with use of such polymerization catalyst.

Other objects and advantages of this invention will be apparent from thedescription given hereinbelow.

The above organotin compound (A) used for the preparation of thecatalyst of this invention may be manufactured by known methods, andthese organotin compounds (A) are known in the art (see, for example,

6 E. Coates, Organometallic Compounds, first pub-.

lished in 1956, Butler & Tanner Ltd., Frome and Lon don). The othercatalyst component (B), namely a complete or partial ester of an oxyacidof phosphorus, its derivative or a combination of reactants capable offorming such ester or derivative, is also known.

The catalyst to be employed in this invention is a heat-reaction productbetween components (A) and (B), which is formed by heating components(A) and (B) while keeping them in contact. For instance, an or-' ganotincompound (A) and a complete or partial ester of an oxyacid of phosphorusor its derivative may be heated together while they are contacted witheach other. When the organotin compound (A) is a compound of formula Iin which X is hydroxy, alkoxy, aryloxy or substituted alkoxy, a compoundof formula II in which X is a polybasic polycarboxylic acid residue,

polyhydric alcohol residue, mercaptoalcohol residue or hydroxycarboxylicacid residue, a compuond of formula III in which Y is oxygen, a compoundof the formula IV in which Y is oxygen or a compuond of the formula V inwhich L and L are oxygen or 0 II C.

the reaction between such organotin compound with a partial ester of anoxyacid of phosphorus is allowed to advance even without heating.Accordingly, in this case, the reaction is effected and then theresulting reaction product is heated to obtain the intended catalyst.

Moreover, it is possible to form a heat-reaction product comprising oneatom or less of phosphorus per atom of tin and heat-react a mixture ofthe heatreaction product with an additional amount of component (B),Furthermore, it is possible to employ as component (B) reactants capableof forming a complete or partial ester of an oxyacid of phosphorus orits derivative, react one of such reactants with the compound (A) andthen react the resulting product with the other reactant. It is alsopossible to react the organotin compound (A) simultaneously with both ofthe esterforming reactants. In case such ester-forming reactants areused as the component (B), it is indispensable to heat at least once asystem in which all of of the organotin compound (A) and theester-forming reactants (B) are contacted with one another. Forinstance, a method may be adapted comprising reacting a compound (A)with one of the ester-forming reactants (B) at room temperature, addingto the system the other esterforming reactant and heating the same, or amethod comprising reacting compound (A) at room temperature successivelywith the ester-forming reactants stepwise, and then heating the totalsystem.

It must be noted that reaction products prepared by all of theabove-mentioned manufacturing procedures are included in the scope ofthe heat-reaction product referred to herein.

According to this invention, the quantitative ratio of the componentsused for the preparation of the catalyst, i.e., the organotin compound(A) and the phosphorus oxyacid ester component (B) may be varied in abroad range. For example, the molar ratio of A B may be varied from I 50to 50 l. A preferable molar ratio ofA b is within a range of from 1 to10: I. When component (B) is a combination of esterforming reactants, itis desired that the amount of phosphorus-containing reactant willsatisfy the above molar ratio requirement, and the other reactant to bereacted with the phosphorus-containing reactant may be used in an amountwithin a broad range, e.g. l 100 molar times the phosphorus-containingreactant.

It is preferred that the reaction between components (A) and (B) isperformed so that the resulting heatreaction product will comprise atleast about one phosphorus atom per atom of tin. A heat-reaction productcomprising phosphorus in an amount of more than one atom per atoms oftin is preferred.

The heat-reaction is usually conducted at temperatures ranging fromabout 80 to about 500C., preferably from about l00 to about 400C.,especially preferably from about l50 to 300C.

This reaction for the preparation of the catalyst is usually conductedin the absence of a solvent, but it is permissible to employ anysuitable solvent. The reaction can be performed in the air, but, ifdesired, it is possible to conduct the reaction in an inert gas such asnitrogen. This procedure is necessary particularly when either component(A) or (B) is readily oxidized or has easily polymerizable functionalgroups. As suitable solvents aliphatic hydrocarbons such as heptane,hexane and kerosine, aromatic hydrocarbons such as benzene and toluene,halogenated aliphatic and aromatic hydrocarbons such as carbontetrachloride, methylene chloride, l,l,l-trichloroethane andchlorobenzene, ethers such as ethyl ether and propyl ether, and ketonessuch as acetone and methylethylketone may be exemalified.

The mechanism of the reaction of forming the catalyst, and the structureof the heat-reaction product have not been completely clarified as yet,but it is presumed that the reaction may progress in a manner ofcondensation while substances of relatively simple structures arereleased as components (A) and (B) are contacted and heated. Forexample, when compound (A) is an alkyltin halide, the volatile materialdistilled off from the reaction system includes alkanes, alkenes,alkanols and alkyl halides.

The heat-reaction product to be employed as the cat- I alyst in thisinvention will now be detailed more specifically by referring to aspecific example.

When tributyltin chloride [(C l-l SnCl] is used as component (A),tributyl phosphate [(C l-l PO is used as component (B), and the twocomponents are reacted at a molar ratio of A B l 2, the resulting solidproduct weighs approximately 55 percent of the total weight of thestarting compounds. When the product is dissolved in benzene andre-precipitated from hexane for purification, by elementary analysis itis confirmed that the purified product contains 34.5 percent of carbonand 6.5 percent of hydrogen. From these values, it is seen that theproduct is very close to 4 9)4 4)2- As described above, the reaction offorming the catalyst of this invention is presumed to progress in amanner of condensation while releasing substances of a simple structure.Thus, a change is observed in the molecular weight of the productdepending on the degree of the progress of the catalyst-formingreaction. More specifically, as the reaction progresses, the averagemolecular weight of the catalyst increases, and finally a product isobtained in the state of a gel which is substantially insoluble. Thecatalytic activity for the polymerization is recognizable in each of theproducts obtained at different stages of the catalyst-forming reaction,i.e., during a period when the reaction product is still soluble and itsmolecular weight is low and even after the product has become insolubleFurther, when any limited portion of the reaction product is isolated bymeans of fractional precipitation, it exhibits catalytic activity.

However, products obtained at different stages of the catalyst-formingreaction do not always exhibit a similar catalytic activity. The reasonis that the degree of the condensation in the heat-reaction product maypresumably influence its catalytic activity. The suitable degree of thecondensation varies depending on the kinds of components (A) and (B),the reacting ratio thereof and other factors, and it can be readilydetermined based on experimental results. For instance, in theabove-mentioned specific example of the reaction product obtained byselecting tributyltin chloride and tributyl hphosphate as components (A)and (B) and reacting them at the molar ratio of A B l 2, a prodnet inwhich the condensation progresses such that the carbon contentdetermined by the elementary analysis is within a range of about 20 toabout 38 percent exhibits good catalytic acitivity, and a tendency ofdecline of the catalytic activity is observed in either a product of alower condensation degree, i.e., a higher carbon content, or a productof a higher condensation degree, i.e., a lower carbon content.

The resulting reaction product may be used as a catalyst as it iswithout further processing. if desired, however, the as-prepared productmay be subjected to a suitable post-treatment, such as heating underreduced pressure, so as to remove unreacted esters, by-products andother volatile substances. The product also may be purified byconventional techniques such as washing with a suitable solvent, ordissolution and reprecipitation, and it may be ground prior to use. Whenthe catalyst is partially soluble in an aromatic hydrocarobn, analiphatic ether, a halogenated hydrocarbon or the like, depending on thedegree of condensation, the soluble portion alone may be separated insuch solvent and used as the catalyst as it is in the solution form orit may be used after the removal of the solvent by maintaining thesolution under reduced pressure or heating it under reduced pressure.Further, such solvent solution of the soluble portion of the product maybe incorporated with a suitable non-solvent to reprecipitate the solidto be used as a catalyst. It is also possible to remove the solubleportion and use the insoluble portion along as a catlyyst. As thesolvent suitably used for separating the soluble portion from thereaction product, aromatic hydrocarbons such as benzene and toluene, andhalogenated hydrocarbons such as chloroform and methylene chloride maybe named. Examples of the non-solvent to be used for precipitation arehexane, heptane and acetone.

The catalyst of this invention exhibits excellent stability and can bestored in the presence of air for a long period without any substantialreduction in its catalytic activity. In case moisture absorption isobserved in the catalyst, the activity of the catalyst can be easilyregenerated by heating the catalyst under reduced pressure. The presenceof a very minor amount of the catalyst is effective for quicklypolymerizing various alkylene oxides, especially vicinal alkyleneoxides, at low temperatures below 30C. to high degrees ofpolymerization. For example, while a catalyst composed mainly oforganoaluminum, one of conventional catalysts most usefulforpolymerization of alkylene oxides, is normally used in an amount of1- 5 percent by weight based on the monomer to be polymerized, the useof the catalyst of this invention in such a small amount as 0.5 0.01percent by weight based on the monomer or less is sufficient to advancethe polymerization at sufficiently practical rates. Furthermore, thecatalyst of this invention can be used in the state exposed to air withsubstantially no degradation of its catalytic activity, unlikeconventional organoaluminum catalysts which are difficult to handle.Moreover, even if the catalyst is left in the resulting polymer, it hasno practical adverse effect on the physical properties of the polymerbecause the amount of catalyst used is very small, and the catalyst neednot be removed from the polymer by additional procedures.

In this invention, sufficient results can be attained by using thecatalyst in an amount of 0.5 0.001 percent by weight based on thealkylene oxide monomer, as described hereinabove. If desired, thecatalyst may used in a greater amount. For instance, the catalyst may beused in an amount of 0.001 5.0 percent by weight, preferably 0.01 2.0percent by weight, more preferably less than 1.0 percent by weight. Inmost usual cases, the catalyst is used in an amount ranging from 0.05percent by weight to 0.5 percent by weight, based on the alkylene oxidemonomer.

Among the organotin compound (A) to be used for the catalyst preparationin accordance with this invention, as to the compound of formula 1,those in which R is selected from the group consisting of alkyl of oneto eight carbon atoms, (ii) alkenyl of two to four carbon atoms, (iii)phenyl or naphthyl, (iv) phenyl or naphthyl substituted by alkyl of oneto four carbon atoms, especially substituted by methyl, (V) cycloalkylof five to six carbon atoms and (vi) phenyl-substituted lower alkyl (forexample, benzyl and phenylethyl); and X is selected from the groupconsisting of hydrogen, halogen, hydroxy, alkoxy of one to 20 carbonatoms, phenoxy or naphthoxy or phenoxy substituted by lower alkyl of oneto three carbon atoms, acyloxy derived from fatty acid of one to 18carbon atoms, alkylthio of one to 12 carbon atoms, phenylthio,naphthylthio, methyl-substituted phenylthio or naphthylthio, alkylthioof one to 12 carbon atoms, especially one to eight carbon atoms,substituted by alkoxycarbonyl having one to four carbon atoms in thealkoxy moiety, alkylthio of one to 12 carbon atoms, especially one toeight carbon atoms, substituted by hydroxy, alkylthio of one to 12carbon atoms, especially one to eight carbon atoms, substituted byacyloxy derived from fatty acid of one to 18 carbon atoms, alkoxy of oneto 12 carbon atoms, especially one to eight carbon atoms, substituted byalkoxycarbonyl having one to four carbon atoms in the alkoxy moiety,alkoxy of one to 12 carbon atoms, especially one to eight carbon atoms,substituted by hydroxy, acyloxy of one to eight carbon atoms substitutedby hydroxy, alkoxy of one to 12 carbon atoms, especially one to eightcarbon atoms, substituted by acyloxy derived from fatty acid of one to18 carbon atoms, acyloxy substituted by alkoxycarbonyl having one toeight carbon atoms in the alkoxy moiety, and acyloxy of one 18 carbonatoms substituted by acyloxy derived from fatty acid of one to 18 carbonatoms are preferred.

The following organotin compounds are examples of the compounds offormula I:

(C4HB)QSI1 0 oo OH=CHCO 0 04m,

C4HgSn( )3, iso- CH =CHSn(OCOCl-l cyclo-C H Sn(OCOCl-l 3 )a iz za a s )au s (Cl-[FCHhSnSCJ-h, a Qa u hs,

SCH;

(C 119): Sn( S- CH-C 0 O C4Ha)2, (CI-102s n zhoCHa S-CHz,

S C4Ho 4Ho)2 O CrzHzs s o moii oob 6533: A

( M, ah

SCH CHr-OCO 0101121 OC;H0

, (cycIo-C 511102311 (CH2=CH)2S11 flflsh ll SCzHs /Br (t 2-0 H ):s

Amon "dhibdrindbTfBiiifiil"if thbs' 'in which R is a member selectedfrom those recited above as R and X with respect to the formula I, and Xis selected from the group consisrinf of carbonic radical; radical of aphosphorus oxyacid selected from phosphoric radical, phosphonic radicaland partially esterified phosphoric acid radical; radical of a dibasiccarboxylic acid of two to 12 carbon atoms; radical of a tribasiccarboxylic acid of three to 12 carbon atoms; radical of atetracarboxylic acid of four to 12 carbon atoms; a polybasicpolycarboxylic acid residue derived from a homopolymer of an unsaturatedcarboxylic acid or a copolymer of an unsaturated carboxylic acid with avinyl monomer, especially a polybasic polycarboxylic acid residuederived from a homopolymer of acrylic or methacrylic acid or a copolymerthereof with a vinyl monomer (e.g., ethylene, allyl esters, vinyl estersand halogenated allyl), a copolymer of maleic or fumaric acid with suchvinyl monomer, and a copolymer of acrylic or methacrylic acid, maleic orfumaric acid and such vinyl monomer; a polyhydric alcohol residue of twoto four carbon atoms; a polythiol residue of two to four carbon atoms; amercaptocarboxylic acid residue of two to 18 carbon atoms; and ahydroxycarboxylic acid residue of two to eight carbon atoms arepreferred.

As examples of such compounds represented by for- Among compounds offormula III those in which R is a member selected from those recitedabove with respect to the formula I and Y stands for oxygen arepreferred. Examples of such compounds are as follows:

LII

Among compounds of formula V those in which R is a member selected fromthose recited above with respect to the formula I and M is selected fromCI-I- --CH, +CHg-l-Q, (in which x is an integer of 1 [O and which y isan integer of ,1 to 3) are preferred.

As such compounds of formula V, the following may be exemplified:

In the invention, the esterified products of oxyacids of phosphorus orderivatives thereof of formulae 1, 2,

6 and the product-forming reactants are the most preferred compounds (B)to be reacted with the organotin compound (A) to form the catalyst.

Referring to the formulae 6 through 10, Z is a member selected from thegroup consisting of alkyl of one to eight carbons and phenyl.

Also as the organic radicals to form the ester, i.e. P-OC linkage in thecompletely or partially esterified oxyacids of phosphorous orderivatives thereof of formulae 1 through 10, optionallyhalogen-substituted, alkyl or alkenyl of one to 12 carbons, which arepreferably chlorineor bromine-substituted; optionallyhalogen-substituted aryl, which are preferably chlorineorbromine-substituted phenyl or tolyl; and optionally alkyl-substitutedcyclohexyl; may be named. When more than one of such organic radical ispresent within a same molecule, they may be the same or different. Alsowhen compound (B) is a partially esterified product, the non-esterifiedhydroxyl radicals may form an acid anhydride, together with monoorpoly-carboxylic acid.

As examples of such completely or partially esterified oxyacids ofphosphorus and derivatives thereof, the following compounds may benamed.

a )z. s 5)2 s), a 5) z 5). 3'( 5) 5)- In this invention, as component(B) a combination of reactants capable of forming the above-mentionedcomplete or partial esters of phosphorus oxyacids or derivatives thereofmay be used. In this case, combinations of at least onephosphorus-containing compound selected from the group consisting ofphosphorus compounds containing at least one P-X linkage (in which Xstands for a halogen atom) in the molecule, phosphorus compoundscontaining at least one P-OH linkage in the molecule and phosphorusoxides such as P 0 P 0 and P 0 with at least one member capable offorming the PO-C linkage by reacting with the phosphorus-containingcompound, which is selected from the group consisting of monoandpolyhydric alcohols which may be substituted by halogen, phenols,epoxides and ethylenically unsaturated compounds are used.

Preferable examples of such combination of esterforming reactants are asfollows:

i. A combination of a phosphorus-containing compound having at least oneP-X linkage (in which X stands for a halogen atom) in the molecule witha member selected from the group consisting of saturated and unsaturatedalcohols of one to 12 carbon atoms, halogen-substituted, saturated andunsaturated alcohols of one to 12 carbon atoms, polyhydric alcohols oftwo to six carbon atoms, alkyl and cycloalkyl epoxides of two to sixcarbon atoms, and phenols.

ii. A combination of a phosphorus-containing compound having at leastone P-OH linkage in the molecule with a member selected from the groupconsisting of olefins of one to l2 carbon atoms, olefins of one to 12carbon atoms substituted by halogen, hydroxy or alkoxy, cyclic olefinsof five to eight carbon atoms, alkyl and cycloalkyl epoxides of two tosix carbon atoms, saturated and unsaturated alcohols of one to 12 carbonatoms, halogensubstituted, saturated and unsaturated alcohols of one to12 carbon atoms, and polyhydric alcohols of two to six carbon atoms.

iii. A combination of a phosphorus oxide, preferably phosphoricanhydride, with a member selected from the group consisting of saturatedand unsaturated alcohols of one to 12 carbon atoms, andhalogen-substituted, saturated and unsaturated alcohols of one to 12carbon atoms.

As the phosphorus-containing compound having at least one P-X linkage inthe molecule, the following compounds may be exemplified:

K571i? an troms-emailing camssasaima at least one P-OH linkage in themolecule, oxyacids of phosphorus and derivatives thereof expressed bythe formulae 1 to 10, and their partially esterified products may beexemplified. As the phosphorus oxide P 0 P 0 and P 0, may be mentioned,P 0 being especially preferred.

As the other reactant to be combined with such phosphorus containingreactant, aliphatic alcohols of one to 12 carbon atoms, which may besubstituted by halogen, Such as CHgOH, C2H5OH4, C3H7OH,iSOC3H1OH may beexemplified, iso C H Ol-l, sec C H OH, C H OH, iso C H OH, C H OH, C HOH may be exemplified, CyClO CQHUOH, CgHuOH, C l-l Cl-l,OI-l,andClCl-l,-Cl-l,0l-l; polyhydric alcohols of two to six carbon atoms suchas HOCl-l,C -l 0I-l,

17 iiooin fiiififc fii ofi cilififi ifioilfYEIFEE fiE $11. Am (SH 511$11 4 $11 6H $11 $1 I-IO-CI-hCFlOCI-IQCFIQCTI, '7 CZ C HQCI I L "andHOCHgCHgOCHgCHgOCHgCHgOH; alkyl and cycloalkyl epoxides of two to sixcarbon atoms such as C=CH1 CH=CH1 and and henols such aS'CII-IQGi-I,"drES CEC HDH, meta-CH C l-l OI-I, para-CH C I-I OI-I andHO-Q-iQ-OH.

I Ha In this inventiomthe polymerization of vicinal alkylene oxides canbe performed in the presence of the catalyst in a manner as adopted inthe conventional process. Since the catalyst of this invention possessesa very high stability and exhibits an activity of a very high level, thepolymerization operation is greatly facili-' tated, and thereproducibility of the reaction is extremely excellent.

Various vicinal alkylene oxides can be homopolymerized or co-polymerizedby the activity of the catalyst of this invention. The vicinal alkyleneoxides polymerizable by the activity of the catalyst of this inventioninclude alkene oxides such as ethylene oxide, propylene oxide, l-buteneoxide, 2-butene oxide, isobutene oxide, butadiene monoxide, l-hexeneoxide and l-octene oxide; cycloalkyl epoxides such as cyclohexene oxideand vinylcyclohexene monoxide; aromatic substituted epoxides such asstyrene oxide and a-methylstyrene oxide; halogen-substituted alkeneoxides such as epifluorohydrin, epibromohydrin, epichlorohydrin,epiiodohydrin and methyl epichlorohydrin (methally chloride epoxide);halogen-substituted aromatic epoxides such as p-chlorostyrene oxide;alkyl or alkenyl glycidyl ethers such as methyl glycidyl ether, ethylglycidyl ether, propyl glycidyl ether, butyl glycidyl ethers, allylglycidyl ethers and chloroethyl glycidyl ether; cycloalkyl glycidylethers such as cyclohexyl glycidyl ether and cyclohexenyl glycidylether; aromatic glycidyl ethers such as phenyl glycidyl ether, tolylglycidyl ether and p-chlorophenyl glycidyl ether; glycidyl esters suchas those of acetic acid, acrylic acid, methacrylic acid and benzoicacid; diepoxides such as vinylcyclohexene dioxide and butadiene dioxide;and diglycidyl ethers such as a reaction product of bis-phenol andepichlorohydrin.

In this invention, the polymerization temperature is not critical. Forexample, the process can be worked at temperatures of such a broad rangeas from 30C. to C. However, since the catalyst of this inventionexhibits a high activity at relatively low temperatures, usually thereaction is performed at 0C. to 50C.

In this invention, a solvent may be optionally present in thepolymerization system. A great variety of solvents can be used in thisinvention. For example, aliphatic hydrocarbons such as heptane,kerosene, nparaffin and hexane; aromatic hydrocarbons such as benzeneand toluene; halogenated hydrocarbons such as methylene chloride,chloroform, carbon tetrachloride and mono-chlorobenzene; ketones such asacetone and methyl ethyl ketone; nitriles such as acetonitrile; etherssuch as diethyl ether, di-isopropyl ether, di-npropyl ether, di-n-butylether, tetrahydrofuran and dioxane; nitrated hydrocarbons such asnitromethane, nitroethane and nitrobenzene; and esters such as ethylacetate, butyl acetate and butyl phthalate may be employed.

The reaction pressure may be atmospheric pressure, or reduced orelevated pressure, inclusive of an autogeneous pressure. Usually,pressures ranging from atmospheric pressure to 50 kg/cm are employed.

Embodiments of preparation of catalysts of this invention and ofpolymerization of alkylene oxides with use of such catalysts will now beexplained by referring to examples.

Examples 1 to 72 Preparation of Catalysts In Examples 1 through 72, thepreparation of catalysts from combinations of various organotincompounds and esters of oxyacids of phosphorus or derivatives thereofare illustrated. The general method of the preparation was as follows:

An organotin compound and an ester of a phosphorus oxyacid or aderivative thereof was placed in a glass reactor of 500 ml or othersuitable capacity with a distilling short column, which was equippedwith a stirring means, a heating device and a thermometer, and stirredunder heating. The volatile material released was distilled off. Thetemperature was raised to approximately 280C. at the highest, butnormally to around 250C. The reaction took place violently, while alarge amount of volatile material was being distilled off. When one ofthe reactants was solid and could not readily be mixed with, ordissolved in, the other homogeneously, the system was heated to attain ahomogeneous state. A portion of the distillate was liquefied by coolingwith ice water. Unless otherwise specified, the reaction was practisedin air. In most'cases, the reaction products were brittle, glassysolids.

The reaction products were treated according to any of the followingtreating method I to 5, and used as the catalyst.

l. The product was allowed to cool, ground and used as it was.

2. The product was allowed to cool, ground and heated at 150C. for 2hours under a reduced pressure of 0.1 mm Hg.

' 3. TlTe rTrtidu ct was aiiaaea meson g'rsan'a', washed 20 with hexaneand dried in vacuo.

4. The product was allowed to coolpground, washed with ether and driedin vacuo.

5. The product was dissolved in benzene, re-

precipitated by the addition of approximately 5 volume times of hexaneand dried in vacuo.

Reactants used in the catalyst preparation and reaction conditionsadopted are given in Table 1. Notes a. In Examples 1, 2, 3, 7, 15, 28,29, 30, 31, 32, 40

and 68, the treatment was conducted in N atmosphere.

b. In Example 51, the reactants (A) and (B) were mixed in benzene.

c. In Examples 10, 57 and 58, the reactants (A) and (B) were mixed inmethylene dichloride.

d. In Example 62, the reactants (A) and (B) were mixed in carbontetrachloride, and the reaction was conducted in N atmosphere.

e. In Example 63, the reactants (A) and (B) were mixed in carbontetrachloride.

f. In Example 69, the reactants (A) and (B) were mixed in ethyl ether.

Organotin compound (A) Esters of oxyacid of phosphorus and derivativesthereof (B) Reaction conditions Max. Example Amount, Amount, Time, temp,Treatnumber Formula grams Formula grams in. 0, m;

1 a)2 2 21. 9 (nCiHahP O4 53. 2 8 260 1 2 (Cz m cl 12 (CiH5)aP0a 23. 210 270 2 3 CflHfiSIlClZ! 25. 3 (isO C4Hv)aPO4 53. 2 8 265 3 4 (isoCaH1)a 1 2 CsH11)aPO4 43. 3 10 265 5 5 (11C4H9)3SI1C1 104 (HC4HB)3PO4168. 8 6 265 2 6 C4Hv):SnC1 104 (IICiHQaPOi 168. 8 6 265 5 7 C4Ho)aS CI5. (CH2=CH CH2)3PO4 6. 8 15 180 3 8 (nOflElmSnCl 5. 0 (C2 )4 201 9. 0 6260 3 9 (I1C4H0)3SI1C1 5. 0 (nC4H (C 113C 0) P04 7. 8 5 260 3 '10(l'lCiHtMSl'lClz 6.1 C4 031 04 10.8 10 260 3 11 1104110311013 5. 6(HC4HO)3PO4 10. 8 8 260 2 12 nC4HoSIlC13 5. 6 (180 C4Hq)sPO4 10. 8 8 2602 13 (nC4Ho)3SnF 20 (110411 P04 35, 5 10 2 0 1 14 (110 1-117) I1 20(nCrHnhPOt 18. 1 6 260 1 15 (CsH5)3Sl1Cl 38 CuHsPO (00211.02 4. 2 10 2403 16 oHshSnIM 6. 2 4 B)3PO( 5. 4 10 260 1 17 (CeH5)2SI1Cl2 3. 4 (n 4BhHPO4 4. 2 10 260 4 18 CsHsSHCl; 3O (I'lC4Hu) P O4 53. 2 8 260 3 19(CaHs)4$ 8. 6 (11C4HD)3P04 10. 6 10 280 1 20 (110411028110 12. 4(nCgHrDaPO; 43. 4 10 280 3 21 (11C5H11)2SI1O 18 (HC4H9)5PO4 26. 6 10 2803 22.... (CuH5)2sI1O 14. 4 (DC4H0)3PO4 26. 6 10 280 1 23.-

5 ll)3 O l1( 5 1l)3 6.8 (110411931 04 10.8 8 250 2 24(CzH5)2BISnOSIl(C2H5)zBr 4. 5 (nC4Hn)3PO4 9. 2 6 250 2 25.. (nC4H)2Sn(OCOCH:)z 17.5 (1'1C4H9) PO4 26. 6 8 260 2 26 CHsSIlOg/ 3. 2(IIC4H9)3PO4 10. 8 8 260 1' /O C O C H 27 (IlCiHg); S n 8. 0 (IIC4H9) 3PO4 6. 3 8 260 2 O C O C H (CuHQzSnS 6. 0 (110411031? 04 5. 4 10 280 3(nC4H )2Sn(SC4Hn)z 4. 1 (IIC4H )3PO4 5. 4 10 280 4 (CuH5C H2)2Sl'l(0CH3): 6. 8 (1104130) 3P0; 10. 8 10 260 2 (HCqHphStKOCqHQ: 4.2(nC4Hn)aP04 5.4 10 260 4 (00110351111 3. 5 (IIC|H9)3PO4 7. 0 10 280 1(CzH5)3Sl1OH 2. 2 (I1C4H9)3PO4 5. 2 12 260 4 34 (C12H23)3 I1C1 13. 0(I1-C4H9) 3P0; 10.8 10 265 3 (CuH5) SnC1 38.4 (H-C4H9)3PO4 53.2 10 270 3(eyclo-C aHnhsncl 20. 1 (ll-C4110) 3P O4 26. 6 10 260 2 (C H5CHD3S11C121.3 (n-C4Hu)3PO4 26.6 10 250 3 (Otl'hD-C HgCnHOa llBI 14. 1(11'C4H0)3PO4 16. 0 8 260 3 (1-C10H1)2SI1C12 4.4 (11'C4HB)3PO4 5.4 8 2603 (CH=CH)SI1C12 4.8 (nC4Hn)3PO4 7.3 5 245 2 (1S0 C4Ha gSI1O 12. 5(II-C4119) JPOJ 26. 6 6 270 2 (CsH5CH hSnO 15.8 (n-C4H03PO4 26.6 8 260 1(cyclo-CiHnhSnO 15. 0 (Ii-C4Hfi3104 26. 6 8 270 2 [(CuH5) SI1]20 3.5(II-C4H9MPO4 4.5 6 260 3 ((C4Ho)aSn(O C 0 CH3) 34. 8 (ti-ciHmPOi 53. 210 240 4 (c4119) Sn(SCHzC 0 0 2H5 5. 2 (IL-C4HQ)3PO4 5. 5 10 250 4(CsH51gSI1(OCOCH=CHCOOC2H5)2 22.2 (II-04119031304 26.6 8 260 34H9)2SI1(O C O CilH 2 63.0 (n C Ho)aPO4 53.2 10 24.0 4(C4Ho)2Sn(SCH2COOC2Hs)2 5.2 (II-(141 10 1 04 5.5 10 250 4((CSHI7)2SI1(OCOH 13.4 (n-C H )3PO4 26.6 8 260 3 51. (CsHs)a (OCisHa1)3.1 (Tl-C4HQ)3PO4 2.7 260 4 52 O ctHi 6. 2 (IIC4H PO4 5. 3 8 260 4 (C snh C SiiHza Esters of oxyacid of phosphorus and Organotin compound (A)derivatives thereof (B) Reaction conditions Max. Example Amount, Amount,Time, temp, Treatnumber Formula grams Formula grams min. ment 6a.?nonoasnuooa as iozrnnrol ii 8.0 16 220 1 54...... (cafinh aCH2OSn(C4Ho)a1.5 11031 04 1.0 6 250 4 55 1 31 1. s oz'mnroi 1. s s 250 2 o=o0-sn04H,),

i 1 O=COSln(C4Ho)2 2.0 CH P0 3.2 10 250 2 sn o1r1 ooooH=oHoo0 2 4 L l1HmSn0-(C1Hmsnn 2.3 (CzH5)3PO4 3.6 260 4 8 CHz-CH 3. 6 (C1HQ)3PO4 5. 5 12250 4 L COOSn(C4Ho):1 Jn 59 CH2=CHCH SnBr 2.0 (H'C4H9)3PO4 10.0 10 240 2C1 mSnO 74. 4 (ll-C4110) P0; 159.6 8 265 3 (n CrHohSnO 74. 4 (C4110)aHPOg 126. O 8 260 3 H1=CH)2SI1 1.9 (c1HmHP03 4. 5 6 260 2 H3113 1. 2(C4H0)3HP0:1 10.8 10 260 3 aH'l): s 1)a 3. 2 (C4111) aHPOz 4. 5 10 260 3(C4Ho)aSnCl 16. 2 0111mm) 0 (32115), 26. 2 s 260 2 (04 10181101 16. 2(010211031 04 29.6 8 260 2 67 (CAHO)3SX1C1 20. 0 c11150)(0111110)11=075.0 10 270 4 (C1Ha) SnC1 5.0 (03119 1 0; 6.3 12 210 2 a)a ]2 1 3.5(C4HoO)zP(O)(OH) 8.4 10 260 2 (C4H1)1S (S Gimp 4.1 (C4HnO)zP(O) (OH) 4.2 10 240 4 (Ce s)2SnCl2 3.4 (C4HnO)2P(O) (OH) 4.2 10 260 2 72(CeH5)aSnC1 3. 8 CeH P(O) (0 C2H5)z 4. 2 10 240 3 Reaction time at amaximum temperature. Polymer of a degree of polymerization of about 100.

EEHIBTs'7 3' WO 7 7 7 M 'rormi'ng reactants were charged into a reactorat TFE'EQEaHsEwere 513511611 by tsegafieiarmethoa described above byemploying combinations of esterforming reactants instead of thephosphorus oxyacid ester or derivatives thereof and adopting any of thefollowing three types of reaction:

The phosphorus-containing compound was charged in a reactor togetherwith the organotin compound, and they were reacted for 40-60 minutes bymild heating. Then, the other reactant was added to the reactionmixture, and the heat reaction was conducted.

the same time, they were reacted at room temperature for about 30minutes (while cooling, if required), and the temperature of thereaction mixture was raised to effect the heat reaction.

Reactants used for the catalyst preparation and the reaction conditionsadopted are given in Table 1'.

Notes a. In Examples 73, 74, 75, 76, 89, 90, 92, 93, 95, 96 and 98,methylene dichloride was charged as a solvent in a reactor together withthe reactants.

b. In Examples 77, 78, 83, 84, 85 and 91, ethyl ether was charged as asolvent into a reactor together with the reactants.

c. In Example 79, l,l,l-trichloroethane was charged as a solvent into areactor together with the reactants.

d. In Examples 80 and 8 l, theheat reaction was effected in N gascurrent.

e. in Examples 94 and 100, carbon tetrachloride was charged as asolventinto a reactor together with the rei'ii'f'ffie 11611 c'es'satnaasasaii51'1'1121's1e1 55 actants.

fwd flit flg "W" a. ...to......,

Reaction conditions Organotin compound (A) Esters-forming reactants (B)Max.- Type Example Amount, Amount, Time,* temp, Treatof the numberFormula grams Formula grams min. C. ment reaction P205 1.2 13 (CH;CHCH2)z(C1H5):Sn 2.6 {,SOQHIOH m 10 240 2 1 POEla 3.0 14 uctttmsn roi9.6 57 12 230 1 (111 1P 13 15.4 ciamsncl 16.2 C 137 15 230 a (111)TABLfY-dntinued Reaction conditions Organotin compound (A)Esters-forming reactants (B) Max. Type Amount, Amount, Time, temp.,Treatof the grams Formula min. C. ment reaction Example number Formulagrams viii: (C4H );SnCl

O 4 0 W0 ll ll 0 5 m n 6. w w L 7 2 (iii) P105 {mo-canon 4 (iii) ClHtOH4 O WW0 l HaPO4 {oHFcHomHm 85......... [(C4Hn)a ]20 CeHlaOH u nhS O 3(iii) 87...." (nata-CHgCgHQgSnO 2 (iii) 2 (iii) 92. (CAHQ)2SH(OCOCH3)1 4(iii) PCls 1 {ll-04119011 94 (CtHQa HO M eHOa POBra {momomon 2 (iii) 2(iii) 28 &7

1000...... (C4H9)3SI1OCHzCHzOSIl(C|Ha)3 Reaction time at maximumtemperature. "Equimolar mixture of 2 phosphorus-containing compounds.

7 pared in Exarnples 1 through 32 are shown. The polymerization waseffected in a glass ampule. Fifty ml of propylene oxide and 0.4 g of acatalyst were used in l Ixampleslljl- -l l3 7 ln Examples 101 through113, polymerization results of propylene oxide in the presence of thecatalysts preeach run. The .air in the ampule was substituted bynitrogen gas, or sealed as it was, and allowed to stand at 25C. for48'hours.

Theresults are given in Table .2.

Ill 29 so 112 31 82 113 32 76 0.92

Example 114-137 lnfiExamples 1 14 through 137; results of epichlorohy-TABLEZ 5 9 e xneri e ieae es. etwje l e. ew; 5 Id R d d v Examples138-145 oi e uce iscosity EL Catalyst polymer (g/1007mm" In thoseexamples, yarlous alkylene oinde monomers No. No. Yield(%) benzene) werepolymerized, using the catalysts within the scope 1 96 of thisinvention. The polymerization was performed in 102 5 Ca. 100 3.51 103 780 a glass ampule which was allowed to stand undisturbed. lg; g 33 if;.1122 13. 11.531? shewnfli Ieblqfi. bs 06 I5 89 Examples 146-160 107 I894 3.90 ln'Examples 146-160, copolymerization of alkylene :8: g; 5? 3'2?oxide monomers was performed as indicated in Table no 27 89 3.1g 7 A 5below, in the mannersirnilar to Examples TABLE 3 Cata- Amount AmountAmount Etherly of of of Reaction Reaction insoluble Ex catalyst monomersolvent temp. time polymer, Example number No (g Solvent (ml) C.) (hr.)yield 2 0.5 50 60 64 '3 0.5 30 18 83 5 0. 5 30 ca. 100 5 0. 5 30 20 87.5 5 0. 5 30 20 87. 5 5 0. 5 30 20 73.4 5 0. 5 30 20 61. 0 6 0.05 15 4880.5 6 0. 5 30 20 85 10 0. 5 30 63 12 0.5 .20 85 13 0.2 25 20 90 14 0.225 20 72.5 16 0.2 25 20 17 0. 2 25 20 68 19 0.2 30 72 67.5 20 0.2 30 2082 22 0. 2 30 20 78 23 0. 2 30 20 95 .24 0.2 30 20 92 25 0. 2 30 20 9228 0.2 30 20 90 29 0.2 30 20 30 0.2 30 20 88 2 5 ;plllllitersn i W V N 1TABLE 4 Amount Amount Polymerl- Polymeriof of catzatlon zatlon StateExample Monomonomer Catalyst alyst temp. time Yield Reduced of numbermer (g.) Ex. No. (g.) C.) (hr.) (percent) viscosity polymer 11 6 0. 2 2548 89 "4. Crystalline. 40 6 0.2 25 48 90 3. 91 Rubbery. 40 6 0.4 25 2470 "0. 95 Crystalline. 40 13 0.4 30 48 86 D0. 25 6 0.2 25 48 90 D0. .2511 0.2 25 78 60 Waxy.

10 5 0.1 50 78 43 Crystalline. 40 5 0.4 50 78 Gelled Benzene 40 ml. 0.5g./ ml. 30 C. aqeuous solution. "1 g./100 m1. 50 C. benzene solution."*1 g./100 ml. 80 C. monochlorobenzene solution. NOTE-E02 Ethyleneoxide; BO: l-butene oxide; 50: Styrene oxide; P GE: Phenylglycldylether; 13 GE: n-Butylglycidyl ether BQJsebatme9;?912359E 925yleyleyeleiei i TABLE 5 Polymeri- Polymeri- Amount zation zation Polymer Amount ofCatalyst of catalyst temp. time yie Ex. No. Monomers monomers (g.) Ex.No 0.) (hr.) (percent) Reduced viscosity 146 EO:EpOH 3 0.1 30 24 88,147- EO:EpCH 6 0.03 20 7 18 3.4 (Cl content 26.0). 148. POzEpCH 12 0.0520 48 Ca.100 149- PO:EpCH 6 0.05 20 48 Ca. 100 150- PO:EpCH 6 0.05 20 48Ca. 100...- 151- PO:EpCH 6 0.5 20 48 86 152- POzEpCH 6 0.5 20 48 153.PO2AGE 5 0.3 25 120 91 Rubbcry. 154. lO:PGE 0 0.2 25 80 Do. 155 lOzll'iO6 0.1 30 24 Do. 150. ltpUlhlllU 0 0.1 50 24 Do. 157. EpUllzllO (l 0.131), 24 D0. 153. l():828 l 0.2 50 48 150 EpCllz828 1 0.2 50 48EpCIINCIIDO 1 0.2 50 48 0.1 g./100 ml., 50 C. cyelo hexamano solution.llggikf to 8218: prodiltiietsEofglliellslnternatlonal Chemicals Corp.,U.K.); Norm-AGE: A1lylglyeidylotl1er;282r Diglycidyl ther (tl' egrgx e vV f 3 f; 7, i .EFPPPWTZ or Examples 161 230 in these examples, resultsof the polymerization or copolymerization of several monomers with useof vari- 28 methylene-bis-(4-methyl-6-tert.-butylphenol).

Results are shown in Table 6.

ous catalysts are illustrated. TABLE 6 In the homopolymerization ofethylene oxide (E) Ex. Catalyst Polymer Reduced (Examples 161 l75), 015part of the catalyst was :21 22 $5 "12? used per 100 parts of a 20percent by weight solution 162 37 81 11:6 of E0 in a solvent indicatedin Table 6, and the reac- :2: I: i: I: 33 2'2 tion was conducted at 30C.for 20 hours. The reduced 165 s1 66 6:3 viscosity of the resultingpolymer was determined with 10 :23 I: g: I: Z3 33 respect to an aqueoussolution of a polymer concentra- I68 u 57 76 1 tion of 0.1 g/l00 ml at35C. I: 65 Ca In the homopolymerization of propylene oxide (PO)- u g:2:: (Examples 176 190), 0.3 part of the catalyst was used 172 76 Ca 10027.0 per 100 parts of a 50 percent by weight solution of P0 :8 .i a: '002) in benzene, and the reaction was conducted at 30C for 17s 93 Ca 10026.0 20 hours. The reduced viscosity of the resulting polyf g; 91 g: merwas determined with respect to a solution of 0.1 78 45 133 6:8 g/ 100 mlpolymer in benzene (containing 0.5 percent I: 49 I: 59 of2,2'-methylenebis-(4-methyl-6-tert.-butylphenol) 20 u $2 al In thehomopolymerization of epichlorohydrin 182 63 I: 54 (EpCl-l) (Examples191 210 l-butene oxide (BO)- {23 g3 Z3 2;; (Example 21 l 214), phenylglycidyl ether (PGE)(Ex- I85 71 60 6.5 amples 215 218) and styrene oxide(SO) (Examples :33 Z 22 's 2l9 222), the bulk polymerization method was25 13s 87 u 80 9:1 adopted unless otherwise indicated. The amount of the:38 I: g: g; 5-; catalyst used was 0.1 part per 100 parts of the mono-19] 5pc 45 mer in the case of the bulk polymerization and 0.3 part I92I: 36 :2 40 per 100 part of the monomer in the case of the solution :33j; ii :18 polymerization. 30 19s 46 36 In the case of EpCl-I, B0 andPGE, the reaction was :3? g3 z: i-gg conducted at 30C. for 30 hours, andin the case of SO, [98 53 38 the reaction was effected at C. for 30hours. 53 32 The reduced viscosity of the resulting polymer was :8? 2gg; determined with respect to a benzene solution of a 35 202 69 48 1.55polymer concentration of 0.1 g/lOO ml at 30C. in the 28: I: I: :2 1 0case of B0, and to a monochlorobenzene solution ofa 205 77 31 polymerconcentration of 0.1 g/lOO ml at 80C. in the :3? E 2 28 case of EpCH,PGE and SO. Each solvent contained 208 .l 31' 57 g? H? 0.5 percent of2,2-methylene-bis-(4-methyl-6-tert.- 40 209 I: 96 j: 3 butylphenol) BOnone 6.0 In the case of the copolymerization (Examples 223 212 59 70 4.7230), the reduced viscosity was determined with re- I: :2 I: 2; 5 5 lspect to a benzene solution of a polymer concentration 215 5 44 u of 0.1g/l00 ml at 30C. in Examples 224 and 227, and 45 216 79 22 with respectto a monochlorobenzene solution of a fi g2" polymer concentration of 0.1g/l00 ml in the other Ex- 219 so 40 42 1.18 amples. Each of the solventscontained 0.5 percent of I: Z: I: the above-mentioned antioxidant,namely 2,2- 222 97 49 0.90

Monomer Catalyst Solvent Polymer Cl amount Catalyst amount amount React.React. yield, Reduced content, Example number Monomers (g) No. (g.)Solvent (g.) Temp. time percent viscosity percent 223 "@8 01 0.00Hexane-.- 22 1s 10 23 2. :10 27.0 P g 92 0. 05 ---d0 20 a0 20 91 120 so0.1 Benzene. 15 so 20 as 1.18 33.4 91 0.1 ...do 15 30 20 41 03 2 s9 0.05 d0 15 30 20 08.100 12.80 2 62 0.05 -do 15 a0 20 gig 88 0. 05 d0 15 a020 9 1.8 23.1 gig as 0.05 -do 15 a0 20 14 2.5 22.2

Partielly gelled.

Norma-GA: Glycidyl acrylate; GMA: Glycidyl mtacrylate.

What we claim is: l. A process for the polymerization of vicinalalkylene oxides, which comprises polymerizing or copolymerizing vicinalalkylene oxides in the presence of a heat-reaction product of (A) anorganotin compound and (B) a complete or partial ester of an oxyacid ofphosphorus, an acetyl derivative of (HO) PO, or a combination ofreactants which form said ester or derivative under the reactionconditions, said organotin compound (A) containing at least onetin-to-carbon bond in its molecule and being selected from the groupconsisting of the compounds of the following formulae (1) through (V):

R SnX wherein R is selected from the group consisting of (i) alkyl ofone to 12 carbon atoms, (ii) alkenyl of two to 12 carbon atoms, (iii)aryl, (iv) aryl substituted by alkyl of one to four carbon atoms, (v)cycloalkyl of three to eight carbon atoms and (vi) aralkyl; X isselected from the group consisting of hydrogen, halogen, hydroxy,alkoxy, aryloxy, acyloxy, alkylthio, arylthio, alkylthio substituted byalkoxycarbonyl, alkylthio substituted by hydroxy, alkylthio substitutedby acyloxy, alkoxy substituted by alkoxycarbonyl, alkoxy substituted byhydroxy, alkoxy substituted by acyloxy, acyloxy substituted byalkoxycarbonyl, acyloxy substituted by hydroxy, acyloxy substituted byacyloxy, aryloxy substituted by alkyl of one to four carbon atoms andarylthio substituted by alkyl of one to four carbon atoms; a is aninteger of 1 through 4; b is an integer of 4 a; and when a is more than1, each R may be the same or different, and when a is 2 and X isselected from the group consisting of alkoxy, acyloxy and alkylthio, thetwo Xs together may form a ring:

a h i in; wherein R is a member selected from the group consisting of Ras defined in formula I and halogen, and at least one R is selected fromR; X is selected from the group consisting of a carbonate radical, anorthophosphate radical,a radical obtained by removal of the carboxylhydrogens from a polycarboxylic acid, polyhydric alcohol residuesobtained by the removal of hydroxyl hydrogens of polyhydric alcohols,alkylene dithio radicals derived from polythiols, mercaptocarboxylicacid residues obtained by removal of carboxylic hydrogen andmercapto-hydrogen from mercapto-carboxylic acids, mercapto-alcoholresidues obtained by removal of hydroxyl hydrogen and mercapto-hydrogenfrom mercapto-alcohols, and hydroxycarboxylic acid residues obtained byremoval of hydroxyl hydrogen and carboxyl hydrogen fromhydroxycarboxylic acids; and Ms an integer not less than 2 andcorresponding to the basicity of the radical X:

wherein R is as defined above; Y is a member selected from the groupconsisting of oxygen and sulfur atoms; it being permissible for thecompound of formula ill to form a complex with a compound of formula I:

R -l- SnR, Y -l- SnR R' IV wherein R is as defined above and each R isthe same; Y is as defined above; R is a member selected from the groupconsisting of R and X as defined in formula l and may be the same ordifferent; and

4- snR -LML' +1" v wherein R is as defined above and the two Rs must bethe same; L and L, which may be the same or different, are selected fromthe group consisting of oxygen, sulfur, and

6. Z(HO) PO in which Z is a member selected from the group consisting ofalkyl of one to eight carbon atoms and phenyl;

7. Z,(HO)PO in which Z is as defined above;

10. Z,(HO)P in which Z is as defined above, said compound (-8)containing a POC linkage formed of an organic radical selected from thegroup consisting of alkyl of one to 12 carbon atoms, unsaturatedhydrocarbon of two to 12 carbon atoms, halogen substituted alkyl of oneto 12 carbon atoms, unsaturated hydrocarbon of two to 12 carbon atoms,aryl, aralkyl, and cyclohexyl; and when the compound (B) is partiallyesterified, the hydroxyl groups which are not esterified may optionallyform an acid anhydride with a mono-carboxylic acid, said combinations ofreactants capable of forming said esters being selected from the groupconsisting of a combination of a phosphoruscontaining compound having atleast one P-X linkage wherein X represents a halogen atom in themolecule with a member selected from the group consisting of saturatedand unsaturated alcohols of one to 12 carbon atoms, halogen-substituted,saturated and unsaturated alcohols of one to 12 carbon atoms, polyhydricalcohols of two to six carbon atoms, alkyl and cycloalkyl epoxides oftwo to six carbon atoms, and phenols; a combination of aphosphorus-containing compound having at least one P-OH linkage in themolecule with a member selected from the group consisting of olefins ofone to 12 carbon atoms, olefins of one to 12 carbon atoms substituted byhalogen, hydroxy or alkoxy, cyclic olefins of five to eight carbonatoms, alkyl and cycloalkyl epoxides of two to six carbon atoms,saturated and unsaturated alcohols of one to 12 carbon atoms,halogen-substituted, saturated and unsaturated alcohols of one to 12carbon atoms, and polyhydric alcohols of two to six carbon atoms; and acombination of a phosphorus oxide with a member selected from the groupconsisting of saturated and unsaturated alcohols of 1 to 12 carbonatoms, and halogen-substituted, saturated and unsaturated alcohols ofone to 12 carbon atoms.

2. The process of claim 1, wherein the heat-reaction product contains atleast one phosphorus atom per tin atom.

3. The process of claim 1, wherein the heat-reaction product is oneformed by reacting said organotin compound (A) with said esterifiedproduct or said combination of ester-forming reactants (B) by heatingthem at a temperature ranging from SOC. to 500C.

4. The process of claim 1 wherein the heat-reaction product is presentin the polymerization system in an amount of 0.001 to 5.0 percent byweight based on the vicinal alkylene oxide monomer.

5. The process of claim 1, wherein the component (B) is a memberselected from the group consisting of complete and partial alkyl estersof an oxyacid of phosphorus.

2. The process of claim 1, wherein the heat-reaction product contains atleast one phosphorus atom per tin atom.
 3. The process of claim 1,wherein the heat-reaction product is one formed by reacting saidorganotin compound (A) with said esterified product or said combinationof ester-forming reactants (B) by heating them at a temperature rangingfrom 80*C. to 500*C.
 4. The process of claim 1 wherein the heat-reactionproduct is present in the polymerization system in an amount of 0.001 to5.0 percent by weight based on the vicinal alkylene oxide monomer. 4.(HO)3P;
 5. (HO)2POP(OH)2;
 5. The process of claim 1, wherein thecomponent (B) is a member selected from the group consisting of completeand partial alkyl esters of an oxyacid of phosphorus.
 6. Z(HO)2PO inwhich Z is a member selected from the group consisting of alkyl of oneto eight carbon atoms and phenyl;
 7. Z2(HO)PO in which Z is as definedabove;
 9. Z(HO)2P in which Z is as defined above; and
 10. Z2(HO)P inwhich Z is as defined above, said compound (B) containing a P-O-Clinkage formed of an organic radical selected from the group consistingof alkyl of one to 12 carbon atoms, unsaturated hydrocarbon of two to 12carbon atoms, halogen substituted alkyl of one to 12 carbon atoms,unsaturated hydrocarbon of two to 12 carbon atoms, aryl, aralkyl, andcyclohexyl; and when the compound (B) is partially esterified, thehydroxyl groups which are not esterified may optionally form an acidanhydride with a mono-carboxylic acid, said combinations of reactantscapable of forming said esters being selected from the group consistingof a combination of a phosphorus-containing compound having at least oneP-X linkage wherein X represents a halogen atom in the molecule with amember selected from the group consisting of saturated and unsaturatedalcohols of one to 12 carbon atoms, halogen-substituted, saturated andunsaturated alcohols of one to 12 carbon atoms, polyhydric alcohols oftwo to six carbon atoms, alkyl and cycloalkyl epoxides of two to sixcarbon atoms, and phenols; a combination of a phosphorus-containingcompound having at least one P-OH linkage in the molecule with a memberselected from the group consisting of olefins of one to 12 carbon atoms,olefins of one to 12 carbon atoms substituted by halogen, hydroxy oralkoxy, cyclic olefins of five to eight carbon atoms, alkyl andcycloalkyl epoxides of two to six carbon atoms, saturated andunsaturated alcohols of one to 12 carbon atoms, halogen-substituted,saturated and unsaturated alcohols of oNe to 12 carbon atoms, andpolyhydric alcohols of two to six carbon atoms; and a combination of aphosphorus oxide with a member selected from the group consisting ofsaturated and unsaturated alcohols of 1 to 12 carbon atoms, andhalogen-substituted, saturated and unsaturated alcohols of one to 12carbon atoms.